KR102277351B1 - Conversion of alcohols to linear and branched functionalized alkanes - Google Patents

Abstract

Embodiments herein relate to the environmentally friendly conversion of simple alcohols to linear or branched functionalized alkanes by integrated catalysis. The alcohol is first oxidized chemically or enzymatically to the corresponding aldehyde or ketone, followed by aldol condensation using a catalyst to give the corresponding enal or enone. The enal or enone is then optionally hydrogenated using a recyclable heterogeneous metal catalyst, organic catalyst or enzyme to provide a linear or branched functionalized alkane with aldehyde, keto- or alcohol functionality. The process is also iterative and can be extended further by repeating the integrated catalysis to prepare long-chain functionalized alkanes from simple alcohols.

Description

Conversion of alcohols to linear and branched functionalized alkanes

An embodiment of the present invention relates to an environmentally friendly and mild process for converting simple alcohols into functionalized long chain alkanes.

Because today's concern for the environment and climate change is one of the biggest debates and a serious problem of our time; Finding new sustainable technological solutions for the replacement or reduction of fossil-based materials is a huge challenge. ¹ The urges and impetus in these areas have driven the scientific community to face these challenges. In this context, biofuels manufactured from renewable sources are a good alternative with less negative impact compared to fossil-based fuels from an environmental point of view. The conversion of biomass to biofuels is a very attractive goal that is being intensively studied, but difficult to achieve. ² Alcohols such as methanol, ethanol, butanol and isopropanol are preferred starting materials and versatile organic compounds readily accessible from biomass (eg via fermentation, pyrolysis, etc.) and further engineered for use as biofuels can be

Research on the conversion of alcohols to long-chain alkanes has begun to increase. Anbarasan et al. demonstrated the catalytic conversion of extractive fermentation to potential fuel chemicals by integration of chemical catalysis. ⁴ Furthermore, the Groger group presented a mild, step-by-step approach to the synthesis of Guerbet alcohol. ^It is known that 5,6,7 aldehydes can be condensed/oligomerized using organic catalysts. However, the one-pot conversion of alcohols to oligomeric aldehydes is not known. There are examples of the use of heterogeneous catalysis for hydrogenation or oxidation reactions of enal and allylic alcohols, respectively. ^8,9 However, the integration of this type of catalysis into the applications of short-chain alcohols, aldehydes and ketones is hampered by the elevated temperatures required for these applications, often above the boiling points of these short-chain compounds. Furthermore, compatibility problems may occur in the case of a less bulky substrate. Therefore, it is very important to use integrated catalysis to convert simple alcohols to valuable functional alkanes (eg biofuels, guerbet alcohols, synthons) under mild conditions.

It is an object of the present disclosure to synthesize, from simple starting alcohols, long chain linear or branched functionalized alkanes as important synthetic building blocks (synthons) or biofuel components.

Another object of the present disclosure is to provide a one-pot solution of synthesis as described above.

Another object of the present disclosure is to synthesize long chain linear or branched functionalized alkanes from alcohols derived from biomass or other renewable sources.

Another object of the present disclosure is to provide a method of the kind mentioned above, which is advantageous from an environmental and health point of view.

Many more objects will become apparent from a study of the summary of the present disclosure, the detailed description and the numerous presented embodiments exemplified in the included schemes, and the appended claims.

summary

Embodiments herein relate to methods of making biofuel components or valuable synthons from alcohols or other simple alcohols derived from biomass. This strategy involves, in a sequential or one-pot procedure, according to Scheme 1, to convert a simple alcohol as a starting material to a product such as a long-chain alcohol, a long-chain saturated aldehyde or ketone, or a long-chain acetal or ketal, an enzyme-, It is based on using a multicatalytic approach that utilizes and combines organic- and heterogeneous catalysis.

In an embodiment, the process herein can convert the starting alcohol (simple alcohol) by the following steps:

(i) oxidizing the starting alcohol to the corresponding aldehyde or ketone;

(ii) condensing the corresponding aldehyde or ketone with an enal or enon; and

(iii) reducing the enal or enone to a product, wherein the product is an alcohol, aldehyde, ketone, acetal or ketal having a chain longer than that of the starting alcohol.

Scheme 1 - Iterative integration catalysis strategy for the conversion of simple alcohols to more valuable functional alkanes

Simple alcohols are understood herein to be readily available mono- or dialcohols having a linear or branched, saturated or unsaturated carbon chain of 1 to 30 carbon atoms (C1-30). Long-chain functionalized alkanes (or products) are understood herein to be compounds having a carbon chain longer than the carbon chain of the starting material from which said product is produced.

Suitable alcohols that may be used in the oxidation step of the methods herein are RCH ₂ OH or RCH(OH)R ¹ , wherein R is H, alkyl, aryl, alkenyl or a heterocyclic group, and R ¹ is alkyl. ) to be.

In another embodiment, as also shown in Scheme 1, the methods of the embodiments herein can be iteratively applied, wherein the steps of the methods described above can be repeated for the product alcohol, wherein the product alcohol is used as the starting alcohol. It can be converted to products with long chains.

In the process herein, a suitable oxidizing agent may be selected according to the nature of the starting alcohol. The oxidizing agent may be oxygen, air, hydrogen peroxide or sodium hypochlorite. One skilled in the art can determine the nature of the oxidizing agent for a particular starting alcohol.

An oxidation catalyst may be used in the oxidation step. Suitable catalysts may be heterogeneously supported metal catalysts, homogeneous organometallic complexes, metal-free catalysts or enzymes, depending on the nature of the starting alcohol. One skilled in the art can determine the nature of the catalyst for a particular starting alcohol.

Suitable metal-free condensation catalysts or salts thereof can be used for the condensation of the corresponding aldehydes or ketones to enals or enones.

In the reduction step of the process herein, a suitable reducing agent (such as formic acid, H ₂ , ammonium formate or Hantzsch ester) is optionally combined with a suitable heterogeneous or homogeneous metal catalyst, metal-free catalyst or enzyme to convert enal or enone to product can be converted

When the method is carried out in a one-pot manner, the multi-catalytic cascade relay sequence involves combining three stages of enzymatic, organic- and heterogeneous catalysis as described above. The benefits of one-pot synthesis are well known, which require significantly less time and energy and often produce fewer by-products.

Alcohols that can be converted to the corresponding aldehydes or ketones using the methods herein are, for example, methanol, ethanol, propanol, butanol, benzyl alcohol, isopropanol, hexanol, octanol, nonanol, hexadecanol and octadecane. can come Aldehydes that can be converted to enal or enone using the methods herein are, for example, acetaldehyde, formaldehyde, propanal, butanal, pentanal, hexanal, octanal, 2,4-hexadienal, cinnamal. aldehyde or benzylaldehyde.

The starting alcohol may be obtained from renewable sources such as biomass, triglycerides, wood, algae, syngas, or may be produced via fermentation or pyrolysis. The starting alcohol may be a fatty alcohol. Reliance on renewable sources to provide starting materials reduces the environmental impact of the process.

In an alternative embodiment, the methods herein may comprise the steps of:

(i) providing a starting alcohol;

(ii) providing an oxidizing agent such as air, O ₂ , or NaClO;

(iii) optionally an oxidation catalyst system such as TEMPO, CuBr, bpy, NMI, O ₂ ; or TEMPO, HNO ₃ , HCl, O ₂ ; or TEMPO, NaOCl, KBr; or heterogeneously supported metal catalysts (Pd, Ag, Ru, Ir, Fe); or providing a homogeneous catalyst system (Pd, Ag, Ru, Ir, Fe) and converting the starting alcohol into the corresponding aldehyde or ketone in the presence of said oxidation catalyst system;

(iv) providing an amine catalyst system or a salt thereof;

(v) optionally comprising an acid and converting the corresponding aldehyde or ketone into an enal or enone, optionally in the presence of said amine catalyst system or a salt thereof comprising an acid;

(vi) providing a reducing agent such as formic acid, H ₂ or ammonium formate,

(vii) optionally a reduction catalyst, such as a heterogeneously supported metal catalyst (Pd, Ag, Ru, Ir, Fe, Ni or Co), or a homogeneous organometallic complex (Pd, Ag, Ru, Ir, Fe, Ni or Co) ; to provide; reducing enal or enone to product, optionally in the presence of said reduction catalyst.

Embodiments herein relate to environmentally friendly and very mild methods of converting simple alcohols into advanced biofuel compounds or synthons (Scheme 1). Synthetic strategies start with the selective oxidation of alcohols, chemically or enzymatically, to the corresponding aldehydes or ketones, respectively. Furthermore, in the next step, the aldehyde or ketone is condensed with a long-chain unsaturated compound (enal or enone) with the aid of a suitable catalyst (for example an organic catalyst or a salt thereof). The enal or enon is then optionally hydrogenated, either in the presence of a heterogeneous metal catalyst and a suitable reducing agent (such as hydrogen gas, ammonium formate, formic acid), or via enzymatic reduction, to a saturated aldehyde, keto- or alcohol functionalized alkanes. Notably, the steps can be integrated into a one-pot or sequential procedure, which can make the chemical process a more sustainable, time, economical and energy efficient approach. ^{The 3} sequence can also be repeated in an iterative manner, so that the carbon chain of the product can be further extended (Scheme 1).

In Example 1 and Table 1 below, the results from the study of the oxidation step are summarized. Among the oxidation systems tested using oxygen as the oxidizing agent, the combination of TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl), NaOCl, and NaBr has a mild temperature such as 10°C. , gives a shorter reaction time and the highest yield. This illustrates the importance and effectiveness in the selection of a suitable catalyst system for the oxidation of a given starting alcohol.

Conversion of aldehydes to the corresponding enal by condensation or oligomerization can be accomplished using suitable organic catalysts or salts thereof, for example pyrrolidine, proline, ammonium fluoride, ammonium formate or glycine. In some cases, acids such as acetic acid may be used as additives (see Example 2 and Table 2). In order to achieve the desired selectivity (with Enal 2 as the main or only condensation product), the choice of catalyst is essential.

The conversion of unsaturated long-chain linear or branched compounds (enals or enones) to the corresponding saturated long-chain linear or branched products by hydrogenation/reduction was studied in Example 3 and summarized in Table 3. Heterogeneous Pd-catalysts in the presence of H ₂ -gas, and hydrogenases or organic catalysts, have proven to be suitable reduction systems for the reactions studied.

The lessons from the isolated reactions discussed above were applied to a one-pot conversion process according to embodiments herein comprising condensation and reduction steps (see Example 4 and Table 4). The compatibility of the two reactions carried out in a one-pot manner, and implicitly the compatibility and stability of the two catalyst systems, was demonstrated by the high conversion and selectivity observed with various starting alcohols. Furthermore, the stability of the Pd-catalyst as a reduction catalyst was demonstrated in a 5-recycle study (see Example 5 and Table 5), which opened an ecological approach in which the metal catalyst could be recycled.

The one-pot reaction system was also tested for an iterative approach, in which a product produced through conversion of a starting alcohol or aldehyde according to an embodiment herein can be used as a starting material in the process described herein (Scheme 3, run as described in Example 6).

Examples of additional one-pots for the conversion of different alcohols to the corresponding aldehydes, followed by condensation to enal, and subsequent reduction to saturated, branched products, are illustrated in Examples 7 and 8, which are described herein Demonstrates a wide range of methods.

Starting with a simple alcohol, one-pot metal or metal-free oxidation, or alternatively, an enzymatic oxidation step, an organocatalytic condensation step, and finally a heterogeneous metal catalysis, organocatalytic or enzymatic hydrogenation step. Combining with gives a product with a longer chain than that of the starting alcohol, which is an alcohol, aldehyde or ketone, enal or enone, in a selective manner and in excellent yield.

Embodiments herein may use renewable sources as sources of ethanol and other simple alcohols, which sources are biomass, triglycerides, wood, algae or syngas (preferably produced by a gasification process). Furthermore, embodiments herein can be carried out in one pot without any purification of intermediates. In one-pot synthesis, the use of renewable sources of starting materials, organic catalysts, enzymes and recyclable heterogeneous metal catalysts makes the embodiments herein sustainable and environmentally friendly.

The process may start from readily available simple aldehydes or ketones, without the need for a first oxidation step.

Example

common way

¹ H NMR spectra were recorded on a Bruker Avance (500 MHz or 400 MHz) spectrometer. Chemical shifts were reported in ppm from tetramethylsilane with solvent resonance due to incomplete deuterium incorporation as internal standard (CDCl ₃ : δ 7.26 ppm). The data recorded were: chemical shift, multiplicity (s = singlet, d = doublet, q = quartet, br = broad, m = multiplet), and coupling constant (Hz), integral value. ¹³ C NMR spectra were recorded using perfect proton decoupling on a Bruker Avance (125.8 MHz or 100 MHz) spectrometer; Chemical shifts were reported in ppm from tetramethylsilane with solvent resonance as internal standard (CDCl ₃ : δ 77.16 ppm).

Commercial reagents were used as purchased without any further purification. An aluminum sheet silica gel plate (Fluka 60 F254) was used for thin layer chromatography (TLC), and the compound was subjected to irradiation with UV light (254 nm), or phosphomolybdic acid (25 g), Ce(SO ₄ ) ₂ Treatment with a solution of H ₂ 0 (10 g), concentrated H ₂ SO ₄ (60 mL) and H ₂ 0 (940 mL) followed by heating or dipping in _{KMnO 4 -Stain,} It was then visualized by heating or washing the stain with water. Purification of the product was performed by flash column chromatography using silica gel (Fluka 60, particle size 0.040-0.063 mm).

Example 1 - Optimization Study of Oxidation Step (Table 1)

To a microwave vial containing hexanol (102 mg, 1 mmol, 1 equiv), the oxidation system and solvent shown in Table 1 were added, and then the reaction mixture was stirred at the temperature shown in Table 1 for the time shown in Table 1.

Example 2 Optimization Study of Condensation Step (Table 2)

To a microwave vial containing acetaldehyde (88.1 mg, 2 mmol, 1 equiv), the oligomerization catalyst and solvent shown in Table 2 were added, and then the reaction mixture was stirred at room temperature for the time shown in Table 2.

Example 3- Pd-catalyzed hydrogenation step (Table 3)

In a microwave vial containing trans,trans-2,4 hexadienal (9.6 mg, 0.1 mmol) in solvent (1 mL), MCF-AmP-Pd(O) (6.5 mg, 5 mol%) or CPG (25 mg, 5 mol%) or Pd/C (5.3 mg, 5 mol%, 10 wt.%) was added and _{a balloon filled with H 2} -gas was connected to the vial and stirred at room temperature for 3 h.

Example 4 Substrate Ranges for One-Pot Condensation and Hydrogenation (Table 4)

To a dried microwave vial containing the aldehyde (2 mmol, 1 equiv) in toluene (1 mL), pyrrolidine (7.1 mg, 0.1 mmol, 5 mol %) and acetic acid (6.0 mg, 0.1 mmol, 5 mol %) was added. The mixture was then stirred at 60° C. for the time indicated in Table 4. Then, after adding MCF-AmP-Pd(O) (130 mg, 5 mol%), _{a balloon filled with H 2} -gas was connected, and the reaction solution was stirred at room temperature for 3 h.

Example 5- Recycle study of MCF-AmP-Pd(0)-catalyst for hydrogenation reaction (Table 5)

To a microwave vial containing 2-ethyl hexenal (9.6 mg, 0.1 mmol) in toluene (1 mL), MCF-AmP-Pd(O) (6.5 mg, 5 mol%) was added and H ₂ -gas was The filled balloon was connected to the vial and stirred at room temperature for 3 h. The reaction mixture was then centrifuged and the solid heterogeneous catalyst was further washed three times with dichloromethane by centrifugation and dried in vacuo overnight. The dried and recycled MCF-AmP-Pd(O) was then further used in the next cycle.

Example 6- One-pot reaction of acetaldehyde to 2-ethyl-hexanal (Scheme 3)

To a dried microwave vial containing acetaldehyde (88.1 mg, 2 mmol) in toluene (1 mL), pyrrolidine (7.1 mg, 0.1 mmol, 5 mol %) and acetic acid (6.0 mg, 0.1 mmol, 5 mol %) ) was added. The mixture was then stirred at 60 °C for 1.5 h. Then, after adding MCF-AmP-Pd(O) (134 mg, 5 mol%) or Pd/C (106 mg, 5 mol%), _{a balloon filled with H 2} -gas was connected, and the reaction solution was cooled to room temperature. was stirred for 3 h. Then the H ₂ gas was removed, pyrrolidine (7.1 mg, 0.1 mmol, 5 mol%) and acetic acid (6.0 mg, 0.1 mmol, 5 mol%) were added, and the reaction mixture was stirred at 60° C. for 8 h. did. Then, _{a balloon filled with H 2} -gas was connected, and the reaction was continued to stir at room temperature for 6 h.

Scheme 3 - One-pot reaction of acetaldehyde to 2-ethyl-hexanal

Example 7- One-pot multicatalyst strategy for the synthesis of saturated branched compounds starting from hexanol (Schemes 4 and 5)

In a microwave vial containing hexanol (120 mg, 1 mmol, 1 equiv) or octanol (130 mg, 1 mmol, 1 equiv) and Tempo (1.6 mg, 0.01 mmol, 1 mol%), CH ₂ Cl ₂ ( 2.5 mL) was added and the reaction mixture was sonicated for 3 min. Then, the reaction liquid was cooled to 10 degreeC, and it stirred vigorously. Then cooled NaBr (0.1 M, 0.1 mL, 10 mol%) and NaOCl (1.6 M, 2.8 eq, adjusted to pH 9 with _{saturated NaHCO 3 ) were added.} Then, the O ₂ -gas-filled balloon was connected, and the reaction solution was stirred at 10 °C for 10 min. The organic phase was then _{extracted with CH 2} Cl ₂ (3x5 mL) and dried over _{Na 2} SO _{4 .} Then, the solvent was evaporated and the dried reaction mixture was transferred to a microwave vial with toluene (0.5 mL), followed by pyrrolidine (3.4 mg, 0.1 mmol, 5 mol%) and acetic acid (6.0 mg, 0.1 mmol, 5 mol%) was added and the reaction mixture was stirred at 60 °C for 4 h. Then, after the reaction solution was cooled to room temperature, MCF-AmP-Pd(O) (67 mg, 5 mol%) was added thereto, _{a balloon filled with H 2} -gas was connected, and the reaction solution was cooled at room temperature for 4 h stirred for a while.

Scheme 4 - One-pot Multicatalytic Reaction for Synthesis of Saturated Branched Compounds Starting from Hexanol

Scheme 5 - One-pot Multicatalytic Reaction for Synthesis of Saturated Branched Compounds Starting from Octanol

Example 8- One-pot multicatalytic strategy for the synthesis of butyraldehyde starting from ethanol (Scheme 6)

To a microwave vial containing ethanol (46 mg, 1 mmol, 1 equiv) and Tempo (1.6 mg, 0.01 mmol, 1 mol%), CH ₂ Cl ₂ (2.5 mL) was added, and the reaction mixture was sonicated for 3 min. processed. Then, the reaction liquid was cooled to 10 degreeC, and it stirred vigorously. Then cooled NaBr (0.1 M, 0.1 mL, 10 mol%) and NaOCl (1.6 M, 2.8 eq, adjusted to pH 9 with _{saturated NaHCO 3 ) were added.} After that, the O ₂ -gas-filled balloon was connected, and the reaction solution was stirred at 10 °C for 3 h. Then pyrrolidine (3.4 mg, 0.05 mmol, 5 mol%) and acetic acid (3.0 mg, 0.05 mmol, 5 mol%) were added, and the reaction mixture was stirred at room temperature for 3 h. Then, the reaction solution was cooled to room temperature, and then MCF-AmP-Pd(O) (67 mg, 5 mol%) was added, and then _{a balloon filled with H 2} -gas was connected, and the reaction solution was stirred at room temperature for 3 h. stirred for a while.

Scheme 6 - One-pot Multicatalytic Reaction for Synthesis of Butyraldehyde Compounds Starting from Ethanol

Structures of the analyzed intermediates and products:

Embodiments herein may be defined by the following clauses:

1. A method for converting alcohol comprising any one of:

(ia) providing an aldehyde; and (iia) providing the aldehyde as a longer-chain Enal; and (iiia) providing the enal as an aldehyde;

or (ib) providing an aldehyde; and (iib) providing the aldehyde as a longer-chain Enal; and (iiib) providing the enal as an alcohol;

or (ic) providing a ketone; and (iic) providing the ketone as a longer-chain enone; and (iiiic) providing the enone as a ketone;

or (id) providing a ketone; and (iid) providing the ketone as a longer-chain enon; and (iiid) providing the enone as an alcohol;

or (ie) providing an aldehyde; and (iie) providing the aldehyde as a longer-chain enone; and (iii) providing the enone as a ketone;

or (if) providing an aldehyde; and (iif) providing the aldehyde as a longer-chain enone; and (iiif) providing the enone as an alcohol;

or (ig) providing an aldehyde; and (iig) providing the aldehyde as a longer-chain enal; and (iiig) providing the enal as an acetal;

or (ih) providing a ketone; and (iih) providing the ketone as a longer-chain enon; and (iiiic) providing the enone as an acetal.

2. The method according to clause 1, wherein the alcohol group is a primary alcohol, the aldehyde moiety has an R group (R=H, alkyl, aryl, heterocyclic and alkene), and the longer chain enal is an R group (R = H, alkyl, aryl, heterocyclic and alkene) and wherein said aldehyde has R (R = H, alkyl, aryl, heterocyclic and alkene) groups.

3. The method according to clause 1, wherein the alcohol group is a primary alcohol, the aldehyde moiety has an R group (R=H, alkyl, aryl, heterocyclic and alkene), and the longer chain enal is an R group (R = H, alkyl, aryl, heterocyclic and alkene) and wherein said alcohol has R (R = H, alkyl, aryl, heterocyclic and alkene).

4. The method according to clause 1-3, wherein the primary alcohol and aldehyde groups are generated via the sequence according to clauses 1-3.

5. The method according to clause 1, wherein the alcohol group is a secondary alcohol and the keto group has R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups , wherein said longer chain enone has R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups, and wherein said ketone is R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups.

6. Clause 1, wherein the alcohol group is a secondary alcohol and the keto group has R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups , wherein said longer chain enone has R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups, and wherein said alcohol is R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups.

7. A method according to clauses 1, 5-6, wherein the secondary alcohol and keto groups are produced via the sequence according to claims 1, 5 and 6.

8. The method according to clause 1, wherein said alcohol group is a primary alcohol, said aldehyde moiety has an R group (R = H, alkyl, aryl, heterocyclic and alkene), and said longer chain enal is an R group (R = H, alkyl, aryl, heterocyclic and alkene), wherein said acetals are R (R = H, alkyl, aryl, heterocyclic and alkene) groups and R ² (R ² =methyl, ethyl, alkyl) groups how to have

9. according to clause 1, wherein the alcohol group is a secondary alcohol and the keto group has R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups , wherein said longer chain enone has R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl, alkyl) groups, and said acetal is R (R = H, alkyl, aryl, heterocyclic and alkene), R ¹ (R ¹ =methyl, ethyl, alkyl) groups and R ² (R ² =methyl, ethyl, alkyl) groups.

10. A method according to clauses 1-9, wherein the aldehyde, the ketone and the alcohol are provided by: first (i) providing the alcohol; (ii) providing an oxidizing agent (air, H ₂ O ₂ , O ₂ , NaOCl); (iii) optionally providing a catalyst that is a heterogeneously supported metal catalyst or a homogeneous organometallic complex or a metal-free catalyst (mediator); and (iv) oxidizing the alcohol by oxidizing the enzyme (EC 1:10:3:2), optionally in the presence of said catalyst;

next

(v) providing an aldehyde or ketone; (vi) providing a metal-free catalyst system; (vii) optionally including an acid or salt and (vii) converting the aldehyde or ketone in the presence of said catalyst system or salt; (viii) providing an enal or enon; (ix) providing a reducing agent (formic acid, H ₂ , ammonium formate, Hantzsch ester); (x) optionally providing a catalyst that is a heterogeneously supported metal catalyst or a homogeneous organometallic complex or a metal-free catalyst; and (xi) reducing the enzyme to reduce the enal or enon, optionally in the presence of the catalyst; (xii) providing an aldehyde or ketone or alcohol or acetal.

11. Process according to clause 10, wherein the condensation catalyst is an organic catalyst system or a salt.

12. Process according to clause 10, wherein the alcohol group is a primary alcohol and the aldehyde moiety bears an R group (R=H, alkyl, aryl and heterocyclic).

13. The method according to clause 10, wherein the alcohol group is a secondary alcohol and the keto group has R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl and alkyl) groups. Way.

14. Process according to clause 10, wherein the aldehyde is a linear or branched aldehyde and the aldehyde moiety bears an R group (R=H, alkyl, aryl and heterocyclic).

15. Process according to clause 10, wherein said enal is a linear or branched aldehyde and said enal bears the group R (R = H, alkyl, aryl and heterocyclic).

16. The ketone according to clause 10, wherein the ketone is a linear or branched ketone, wherein the ketone comprises R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl and alkyl) groups how to have

17. The enone according to clause 10, wherein the enone is a linear or branched enone, wherein the enone comprises R (R = H, alkyl, aryl, heterocyclic and alkene) and R ¹ (R ¹ =methyl, ethyl and alkyl) groups. how to have

18. Process according to clause 10, wherein said alcohol is methanol, ethanol, propanol, butanol, benzyl alcohol, isopropanol, hexanol, octanol, nonanol, hexadecanol and octadecanol.

19. The method according to clause 10, wherein said alcohol is derived from biomass.

20. The method according to clause 10, wherein said alcohol is derived from triglycerides.

21. The method according to clause 10, wherein said alcohol is derived from a fatty acid.

22. The method according to clause 10, wherein the alcohol is derived from wood.

23. The method according to clause 10, wherein said alcohol is derived from fermentation.

24. The method according to clause 10, wherein the alcohol is derived from wood.

25. The method according to clause 10, wherein said alcohol is derived from algae.

26. The method according to clause 10, wherein the alcohol is derived from a fossil based material.

27. Process according to clause 10, wherein the alcohol is derived from gasification.

28. The method according to clause 10, wherein the alcohol is derived from pyrolysis.

29. Process according to clause 10, wherein said aldehyde is acetaldehyde, formaldehyde, propanal, butanal, pentanal, hexanal, octanal, 2,4-hexadienal, cinnamaldehyde and benzylaldehyde.

30. A method according to clauses 1-9, wherein the aldehyde, ketone, alcohol or acetal is provided by: first (i) providing the alcohol; (ii) providing an oxidizing agent (air, O ₂ , NaOCl); (iii) optionally Tempo, CuBr, bpy, NMI, O ₂ ; or Tempo, HNO ₃ , HCl, O ₂ ; or Tempo, NaOCl, KBr; or heterogeneously supported metal catalysts (Pd, Ag, Ru, Ir, Fe); or providing an oxidation catalyst system which is a homogeneous catalyst system (Pd, Ag, Ru, Ir, Fe) and (iii) converting an alcohol, in the presence of said oxidation catalyst system;

next,

(v) providing an aldehyde or ketone; (vi) providing an amine catalyst system; (vii) optionally including an acid or salt, (vii) converting the aldehyde or ketone in the presence of said catalyst system or salt; (viii) providing an enal or enon; (ix) providing a reducing agent (formic acid, H ₂ , ammonium formate); (x) optionally a heterogeneously supported metal catalyst (Pd, Ag, Ru, Ir, Fe, Ni, Co), or a homogeneous organometallic complex (Pd, Ag, Ru, Ir, Fe, Ni, Co). to do; (xi) reducing the enal or enone, optionally in the presence of said catalyst; (xii) providing an aldehyde or ketone or alcohol or acetal.

Claims (18)

A process for conversion of a starting alcohol, comprising the steps of, wherein the starting alcohol is derived from any of biomass, triglycerides, wood, algae, fossil-based materials and syngas, or the starting alcohol A process for the conversion of a starting alcohol, produced through any of these fermentations and pyrolysis, or wherein the starting alcohol is a fatty alcohol and is carried out in a one-pot procedure without any purification of the intermediate:
(i) oxidizing the starting alcohol to the corresponding aldehyde or ketone, wherein the oxidation is carried out using an oxidizing agent and a catalyst, the oxidizing agent being any one of oxygen, air, hydrogen peroxide and sodium hypochlorite, the catalyst being heterogeneously supported a metal catalyst, a homogeneous organometallic complex, any one of a metal-free catalyst and an enzyme;
(ii) condensing the corresponding aldehyde or ketone to an enal or enon using a metal-free condensation catalyst; and
(iii) reducing the enal or enone to a product using a heterogeneous metal catalyst and a reducing agent, wherein the heterogeneous metal catalyst is a heterogeneous Pd-catalyst, and wherein the product has a longer chain than that of the starting alcohol. , which is an aldehyde, a ketone, an acetal or a ketal. Process according to claim 1, wherein the starting alcohol is a primary alcohol of the formula R-CH ₂ -OH, wherein R is H, alkyl, aryl, alkenyl or a heterocyclic group. The secondary of claim 1 , wherein the starting alcohol is of the formula R—CH(OH)—R ¹ , wherein R is H, alkyl, aryl, alkenyl or a heterocyclic group and R ¹ is alkyl. A method of conversion of a starting alcohol, which is an alcohol. 4. Process according to any one of claims 1 to 3, comprising repeating the steps of claim 1 using the product alcohol as the starting alcohol. 4. The method according to any one of claims 1 to 3, wherein the condensation of the aldehyde is carried out using an organic catalyst or a salt thereof, optionally in the presence of acid or acetic acid, the catalyst being pyrrolidine, proline, ammonium formate or Glycine, a method of conversion of the starting alcohol. Process according to any one of claims 1 to 3, wherein the reduction is _{carried out with a reducing agent which is formic acid, H 2} , ammonium formate or a Hantzsch ester. Process according to any one of the preceding claims, wherein in the reduction step the heterogeneous metal catalyst is a heterogeneous Pd-catalyst and the reducing agent is H _{2 -gas.} Process according to any one of claims 1 to 3, wherein the heterogeneous metal catalyst in the reduction step is MCF-AmP-Pd(O). 4. The process according to any one of claims 1 to 3, comprising the steps of:
(i) providing a starting alcohol;
(ii) providing an oxidizing agent, air, H ₂ O ₂ , O ₂ or NaOCl;
(iii) providing an oxidation catalyst or a heterogeneously supported metal catalyst or a homogeneous organometallic complex or a metal free catalyst (mediator) or an oxidizing enzyme (EC 1:10:3:2), the starting alcohol being dissolved in the presence of the oxidation catalyst , oxidation to the corresponding aldehyde or ketone;
(iv) providing a metal-free condensation catalyst system;
(v) optionally comprising an acid or a salt thereof and converting the corresponding aldehyde or ketone into an enal or enone in the presence of said condensation catalyst system;
(vi) providing a reducing agent, formic acid, H ₂ , ammonium formate or Hantzsch ester,
(vii) providing a reduction catalyst that is a heterogeneous metal catalyst and reducing the enal or enon to a product, optionally in the presence of said reduction catalyst. 10. The process according to claim 9, wherein the condensation catalyst system is an organic catalyst system or a salt thereof. 10. The process according to claim 9, wherein the starting alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, benzyl alcohol, isopropanol, hexanol, octanol, nonanol and octadecanol. 10. The starting alcohol of claim 9, wherein the corresponding aldehyde is acetaldehyde, formaldehyde, propanal, butanal, pentanal, hexanal, octanal, 2,4-hexadienal, cinnamaldehyde or benzylaldehyde. How to switch. 4. The process according to any one of claims 1 to 3, comprising the steps of:
(i) providing a starting alcohol;
(ii) providing an oxidizing agent, air, O ₂ , or NaClO;
(iii) oxidation catalyst systems or TEMPO, CuBr, bpy, NMI, O ₂ ; or TEMPO, HNO ₃ , HCl, O ₂ ; or TEMPO, NaOCl, KBr; or heterogeneously supported metal catalysts (Pd, Ag, Ru, Ir or Fe); or providing a homogeneous catalyst system (Pd, Ag, Ru, Ir or Fe) and converting the starting alcohol into the corresponding aldehyde or ketone in the presence of said oxidation catalyst system;
(iv) providing an amine catalyst system or a salt thereof;
(v) optionally comprising an acid and converting the corresponding aldehyde or ketone into an enal or enone, optionally in the presence of said amine catalyst system or a salt thereof comprising an acid;
(vi) providing a reducing agent, formic acid, H ₂ or ammonium formate,
(vii) providing a reduction catalyst that is a heterogeneous metal catalyst; reducing enal or enone to product, optionally in the presence of said reduction catalyst. The process according to any one of claims 1 to 3, which is carried out in a one-pot procedure without any purification of the intermediate, comprising:
- providing the starting alcohol, which is a microwave vial containing hexanol or octanol (1 mmol),
- oxidation catalyst system, which is _{TEMPO (1 mol %) in CHCl 2} (2.5 ml), sonicated for 3 min, cooled to 10° C. under stirring, followed by cooled NaBr (10 mol %) and NaOCl (2.8 equiv. ) and _{adjusted to pH 9 with saturated NaHCO 3} ), converting the starting alcohol to the corresponding aldehyde or ketone,
- O ₂ - The oxidizer, which is a balloon filled with gas, is provided under stirring at 10° C. for 10 minutes,
- _{extract the organic phase with CHCI 2} (3 x 5 ml), _{dry the reaction mixture over Na 2} SO ₄ , evaporate the solvent and transfer the dried reaction mixture to a microwave vial,
- toluene (0.5 ml) and pyrrolidine (5 mol%) and acetic acid (5 mol%) are added under stirring at 60° C. for 4 h, and the corresponding aldehyde or ketone is converted to an enal or enone,
- Cool to room temperature,
- MCF-AmP-Pd(0) (5 mol%) of reducing catalyst and _{reducing agent, which is a balloon filled with H 2} gas, are added under stirring at room temperature for 4 hours, reducing enal or enone to product. The process according to any one of claims 1 to 3, which is carried out in a one-pot procedure without any purification of the intermediate, comprising:
- providing the starting alcohol, which is a microwave vial containing ethanol (1 mmol),
- oxidation catalyst system, which is _{TEMPO (1 mol %) in CHCl 2} (2.5 ml), sonicated for 3 min, cooled to 10° C. under stirring, followed by cooled NaBr (10 mol %) and NaOCl (2.8 equiv. ) and adjusted to pH 9 with _{saturated NaHCO 3 ),}
- O ₂ - The oxidizing agent, which is a balloon filled with gas, is provided under stirring at 10° C. for 3 hours, the starting alcohol is converted into the corresponding aldehyde or ketone,
- pyrrolidine (5 mol%) and acetic acid (5 mol%) are added under stirring at room temperature for 3 h, and the corresponding aldehyde or ketone is converted to an enal or enone,
- Cool to room temperature,
- MCF-AmP-Pd(0) (5 mol%) reducing catalyst and _{reducing agent, which is a balloon filled with H 2} gas, are added under stirring at room temperature for 3 hours, reducing enal or enone to product. delete delete delete